Compositions containing silicone polymer, wax and volatile solvent

ABSTRACT

The invention relates to compositions containing at least one polyorganosiloxane-containing polymer, at least one volatile non-silicone oil, at least one alkylene polymer wax, at least one silicone film-forming agent and, optionally, at least one long-chain alcohol wax, at least one coloring agent, and/or at least one volatile silicone oil, as well as to methods for using such compositions and to kits containing such compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.11/217,293, filed Sep. 2, 2005, the entire contents of which are herebyincorporated by reference.

FIELD OF THE INVENTION

The present invention relates to compositions comprising at least onepolyorganosiloxane-containing polymer, at least one volatilenon-silicone oil, at least one alkylene polymer wax, at least onesilicone film-forming agent and, optionally, at least one long-chainalcohol wax, at least one coloring agent, and/or at least one volatilesilicone oil, as well as to methods for using such compositions and tokits containing such compositions.

DISCUSSION OF THE BACKGROUND

Many pigmented cosmetic compositions such as foundations, lipsticks andmascaras have been developed for longer wear and transfer resistanceproperties. This is typically accomplished by the use of ingredientsthat form a film after application, ingredients such as silicone filmforming agents. Such compositions generally contain volatile solventswhich evaporate on contact with the skin or other keratinous tissue,leaving behind a film or layer comprising waxes and/or resins, pigments,fillers, and actives.

In the past, it has been problematic to formulate compositionscontaining silicone film forming agents such as silicone resins intocompositions possessing acceptable cosmetic properties such as, forexample, acceptable wear, transfer-resistance, feel, spreadability andstability properties, particularly where the composition was a solidcomposition such as a lipstick or a stick foundation.

Thus, there remains a need for improved compositions containing siliconefilm forming agents such as silicone resins, particularly solidcompositions containing such silicone film-forming agents, which haveacceptable or improved wear, transfer-resistance, feel, spreadabilityand/or stability properties for application to keratin materials such asskin, lips or eyelashes.

Accordingly, one aspect of the present invention is to provide a careand/or makeup and/or treatment composition for keratinous material suchas the skin, hair and/or lips, which is able to address or overcome atleast one of the aforementioned problems with the prior artcompositions, as well as to provide methods for using such compositionsand kits containing such compositions.

SUMMARY OF THE INVENTION

The present invention relates to compositions, preferably long wearingor transfer-resistant make-up compositions, comprising at least onepolyorganosiloxane-containing polymer, at least one volatilenon-silicone oil, at least one alkylene polymer wax and at least onesilicone film forming agent. Preferably, the compositions furthercomprise at least one long-chain alcohol wax, at least one coloringagent, and/or at least one volatile silicone oil. Most preferably, thecompositions further comprise both at least one coloring agent and atleast one long-chain alcohol wax.

The present invention also relates to methods of treating, caring forand/or making up keratinous material (for example, skin) by applyingcompositions of the present invention to the keratinous material in anamount sufficient to treat, care for and/or make up the keratinousmaterial.

The present invention further relates to covering or hiding skin defectsassociated with keratinous material (for example, skin) by applyingcompositions of the present invention to the keratinous material in anamount sufficient to cover or hide such skin defects.

The present invention also relates to methods of enhancing theappearance of keratinous material (for example, skin) by applyingcompositions of the present invention to the keratinous material in anamount sufficient to enhance the appearance of the keratinous material.

The present invention further relates to compositions having improvedcosmetic properties such as, for example, improved long wear, transferresistance and/or waterproof properties. The compositions may alsopossess improved flexibility, wearability, drying time and/or retentionas well as reduced tackiness and/or migration over time.

The present invention also relates to kits comprising a composition,preferably a long wearing or transfer-resistant make-up composition,comprising at least one polyorganosiloxane-containing polymer, at leastone volatile non-silicone oil, at least one alkylenene polymer wax andat least one silicone film forming agent, preferably further comprisingat least one coloring agent, at least one volatile silicone oil and/orat least one long-chain alcohol wax. Such kits can also includeadditional compositions such as, for example, topcoats for applicationto long wearing or transfer resistant make-up compositions or primers(basecoats) for application to keratin materials prior to application ofa long wearing or transfer resistant make-up composition.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the expression “at least one” means one or more and thusincludes individual components as well as mixtures/combinations.

“Film former” or “film forming agent” as used herein means a polymerthat, after dissolution in at least one solvent, leaves a film on thesubstrate to which it is applied, for example, once the at least onesolvent evaporates, absorbs and/or dissipates on the substrate.

“Transfer resistance” as used herein refers to the quality exhibited bycompositions that are not readily removed by contact with anothermaterial, such as, for example, a glass, food, an item of clothing orthe skin, for example, when eating or drinking. Transfer resistance maybe evaluated by any method known in the art for evaluating such. Forexample, transfer resistance of a composition may be evaluated by a“kiss” test. The “kiss” test may involve application of the compositionto human lips followed by “kissing” a material, for example, a sheet ofpaper, after expiration of a certain amount of time followingapplication, such as 2 minutes after application. Similarly, transferresistance of a composition may be evaluated by the amount of producttransferred from a wearer to any other substrate, such as transfer fromthe neck of an individual to a collar after the expiration of a certainamount of time following application. The amount of compositiontransferred to the substrate (e.g., collar, or paper) may then beevaluated and compared. For example, a composition may be transferresistant if a majority of the product is left on the wearer, e.g.,lips, neck, etc. Further, the amount transferred may be compared withthat transferred by other compositions, such as commercially availablecompositions. In a preferred embodiment of the present invention, littleor no composition is transferred to the substrate. Thus,transfer-resistant compositions include transfer-free compositions.

“Long wear” compositions as used herein, refers to compositions where atleast one property chosen from consistency, texture, and color remainsthe same as at the time of application, as viewed by the naked eye,after an extended period of time, such as, for example, 1 hour, 2 hours,and further such as 8 hours. Long wear properties may be evaluated byany method known in the art for evaluating such properties. For example,long wear may be evaluated by a test involving the application of acomposition to human skin (including lips) and evaluating theconsistency, texture and color of the composition after an extendedperiod of time. For example, the consistency, texture and color of a lipcomposition may be evaluated immediately following application and thesecharacteristics may then be re-evaluated and compared after anindividual has worn the lip composition for a certain amount of time.Further, these characteristics may be evaluated with respect to othercompositions, such as commercially available compositions.

“Make-up composition” as used herein means any composition applied tokeratin materials for aesthetic purposes. Examples of acceptable make-upcompositions include, but are not limited to, lip compositions such aslipsticks, liquid lip colors, lip glosses, skin compositions such asstick foundations or compact foundations, fingernail compositions suchas nail polish and eyelash/hair compositions such as mascaras.

The compositions, kits and methods of the present invention cancomprise, consist of, or consist essentially of the essential elementsand limitations of the invention described herein, as well as anyadditional or optional ingredients, components, or limitations describedherein or otherwise useful in personal care compositions intended fortopical application to keratin materials.

The compositions of the present invention may be in any form. Forexample, they may be a paste, a solid, a gel, or a cream. They may be anemulsion, such as an oil-in-water or water-in-oil emulsion, a multipleemulsion, such as an oil-in-water-in-oil emulsion or awater-in-oil-in-water emulsion, or a solid, rigid or supple gel,including anhydrous gels. The compositions can also be in a form chosenfrom a translucent anhydrous gel and a transparent anhydrous gel. Thecompositions of the invention may, for example, comprise an external orcontinuous fatty phase. The compositions may be anhydrous. In anotherembodiment, the compositions of the invention may be transparent orclear. The compositions can also be a molded composition or cast as astick or a dish. The compositions in one embodiment can be a solid suchas a molded stick or a poured stick. The composition can be either solid(for example, a lipstick, a stick foundation or a compact foundation) orliquid (for example, a liquid lip composition, mascara, liquidfoundation or nail polish). Also, the composition can contain water, butit also may be anhydrous, if desired.

According to preferred embodiments of the present invention, thecompositions are solid. The solid nature of the compositions can bedetermined by determining the hardness of the compositions. The hardnessof a composition may, for example, be expressed in gramforce (gf). Solidcompositions of the present invention may, for example, have a hardnessranging from 20 gf to 2000 gf, such as from 20 gf to 900 gf, and furthersuch as from 20 gf to 600 gf.

This hardness is measured in one of two ways. A first test for hardnessis according to a method of penetrating a probe into the composition andin particular using a texture analyzer (for example TA-XT2i from Rheo)equipped with an ebonite cylinder of height 25 mm and diameter 8 mm. Thehardness measurement is carried out at 20° C. at the center of 5 samplesof the composition. The cylinder is introduced into each sample ofcomposition at a pre-speed of 2 mm/s and then at a speed of 0.5 mm/s andfinally at a post-speed of 2 mm/s, the total displacement being 1 mm.The recorded hardness value is that of the maximum peak observed. Themeasurement error is ±50gf.

The second test for hardness is the “cheese wire” method, which involvescutting an 8.1 mm or preferably 12.7 mm in diameter stick compositionand measuring its hardness at 20° C. using a DFGHS 2 tensile testingmachine from Indelco-Chatillon Co. at a speed of 100 mm/minute. Thehardness value from this method is expressed in grams as the shear forcerequired to cut a stick under the above conditions. According to thismethod, the hardness of compositions according to the present inventionwhich may be in stick form may, for example, range from 30 gf to 300 gf,such as from 30 gf to 250 gf, for a sample of 8.1 mm in diameter stick,and further such as from 30 gf to 200 gf, and also further such as from30 gf to 120 gf for a sample of 12.7 mm in diameter stick.

When the compositions are solid, the hardness of the composition of thepresent invention is such that the compositions are self-supporting butcan easily form a satisfactory deposit on a keratinous material. Inaddition, this hardness imparts good impact strength to the inventivecompositions, which can be molded or cast, for example, in stick or dishform.

The skilled artisan may choose to evaluate a composition using at leastone of the tests for hardness outlined above based on the applicationenvisaged and the hardness desired. If one obtains an acceptablehardness value, in view of the intended application, from at least oneof these hardness tests, the composition falls within preferredembodiments of the invention.

As defined herein, stability is tested by placing the composition in acontrolled environment chamber for 8 weeks at 25° C. In this test, thephysical condition of the sample is inspected as it is placed in thechamber. The sample is then inspected again at 24 hours, 3 days, 1 week,2 weeks, 4 weeks and 8 weeks. At each inspection, the sample is examinedfor abnormalities in the composition such as phase separation if thecomposition is in the form of an emulsion, bending or leaning if thecomposition is in stick form, melting, or syneresis (or sweating). Thestability is further tested by repeating the 8-week test at 40° C., 37°C., 45° C., 50° C. and under freeze-thaw conditions. A composition isconsidered to lack stability if in any of these tests an abnormalitythat impedes functioning of the composition is observed. The skilledartisan will readily recognize an abnormality that impedes functioningof a composition based on the intended application.

In accordance with preferred embodiments of the present invention,compositions comprising at least one polyorganosiloxane-containingpolymer, at least one volatile non-silicone oil, at least one alkylenepolymer wax and at least one silicone film forming agent are provided.

Polyorganosiloxane-Containing Polymer

According to preferred embodiments, the composition comprises apolyorganosiloxane-containing polymer. Any polyorganosiloxane-containingpolymer can be used. For example, suitable polyorganosiloxane-containingpolymers include, but are not limited to, thepolyorganosiloxane-containing polymers and copolymers disclosed in U.S.patent application publication no. 2004-0170586, corresponding to U.S.patent application Ser. No. 10/733,467, filed Dec. 10, 2003, herebyincorporated by reference in its entirety.

Preferably, the polyorganosiloxane containing polymer or copolymer is apolysilicone polyamide polymer such as, for example, those disclosed inU.S. Pat. Nos. 5,874,069, 5,919,441, 6,051,216 and 5,981,680, all ofwhich are hereby incorporated by reference in their entirety, and/orthose polymers described below.

Preferred polyorganosiloxane containing polymers are chosen fromhomopolymers and copolymers, preferably, with a weight-average molecularmass ranging from about 500 to about 2.5×10⁶ or more, comprising atleast one moiety comprising: at least one polyorganosiloxane groupcomprising, preferably, from 1 to about 10,000 organosiloxane units inthe chain of the moiety or in the form of a graft, and at least twogroups capable of establishing hydrogen interactions.

According to preferred embodiments of the present invention, thepolyorganosiloxane-containing polymers used in the composition of theinvention may belong to the following two families:

a) polyorganosiloxanes comprising at least two groups capable ofestablishing hydrogen interactions, these two groups being located inthe polymer chain; and/or

b) polyorganosiloxanes comprising at least two groups capable ofestablishing hydrogen interactions, these two groups being located ongrafts or branches.

The polyorganosiloxane containing polymers of the present invention canbe liquid or solid at room temperature. Preferably, the polymers aresolid. When the polymers are solid, it is preferable that they can bedissolved before or during use in a solvent with hydrogen interactioncapable of breaking the hydrogen interactions of the polymers, forinstance C₂ to C₈ lower alcohols and especially ethanol, n-propanol orisopropanol. It is also possible to use these hydrogen interaction“breaking” solvents as co-solvents in the compositions of the presentinvention. These solvents may then be stored in the composition or maybe removed by selective evaporation, which is well known to thoseskilled in the art.

The polymers comprising two groups capable of establishing hydrogeninteractions in the polymer chain may be polymers comprising at leastone moiety corresponding to the formula:

in which:

1) R¹, R², R³ and R⁴, which may be identical or different, represent agroup chosen from:

linear, branched or cyclic, saturated or unsaturated, C₁ to C₄₀hydrocarbon-based groups, possibly containing in their chain one or moreoxygen, sulphur and/or nitrogen atoms, and possibly being partially ortotally substituted with fluorine atoms,

C₆ to C₁₀ aryl groups, optionally substituted with one or more C₁ to C₄alkyl groups,

polyorganosiloxane chains possibly containing one or more oxygen,sulphur and/or nitrogen atoms;

2) the groups X, which may be identical or different, represent a linearor branched C₁ to C₃₀ alkylenediyl group, possibly containing in itschain one or more oxygen and/or nitrogen atoms;

3) Y is a saturated or unsaturated, C₁ to C₅₀ linear or brancheddivalent alkylene, arylene, cycloalkylene, alkylarylene or arylalkylenegroup, possibly comprising one or more oxygen, sulphur and/or nitrogenatoms, and/or bearing as substituent one of the following atoms orgroups of atoms: fluorine, hydroxyl, C₃ to C₈ cycloalkyl, C₁ to C₄₀alkyl, C₅ to C₁₀ aryl, phenyl optionally substituted with 1 to 3 C₁ toC₃ alkyl groups, C₁ to C₃ hydroxyalkyl and C₁ to C₆ aminoalkyl, or

4) Y represents a group corresponding to the formula:

in which

T represents a linear or branched, saturated or unsaturated, C₃ to C₂₄trivalent or tetravalent hydrocarbon-based group optionally substitutedwith a polyorganosiloxane chain, and possibly containing one or moreatoms chosen from 0, N and S, or T represents a trivalent atom chosenfrom N, P and Al, and

R⁵ represents a linear or branched C₁ to C₅₀ alkyl group or apolyorganosiloxane chain, possibly comprising one or more ester, amide,urethane, thiocarbamate, urea, thiourea and/or sulphonamide groups,which may be linked to another chain of the polymer;

5) the groups G, which may be identical or different, represent divalentgroups chosen from:

in which R⁶ represents a hydrogen atom or a linear or branched C₁ to C₂₀alkyl group, on condition that at least 50% of the groups R⁶ of thepolymer represents a hydrogen atom and that at least two of the groups Gof the polymer are a group other than:

6) n is an integer of at least 1, for example ranging from 2 to 500 andpreferably from 2 to 200, and m is an integer of at least one, rangingfrom 1 to 35,000, for example, from 1 to 10,000 and 1 to 2,500, from 1to 700 and from 6 to 200, including all values and subranges therebetween.

According to the invention, 80% of the groups R¹, R², R³ and R⁴ of thepolymer are preferably chosen from methyl, ethyl, phenyl and3,3,3-trifluoropropyl groups.

According to the invention, Y can represent various divalent groups,furthermore optionally comprising one or two free valencies to establishbonds with other moieties of the polymer or copolymer. Preferably, Yrepresents a group chosen from:

a) linear C₁ to C₂₀ and preferably C₁ to C₁₀ alkylene groups,

b) C₃₀ to C₅₆ branched alkylene groups possibly comprising rings andunconjugated unsaturations,

c) C₅-C₆ cycloalkylene groups,

d) phenylene groups optionally substituted with one or more C₁ to C₄₀alkyl groups,

e) C₁ to C₂₀ alkylene groups comprising from 1 to 5 amide groups,

f) C₁ to C₂₀ alkylene groups comprising one or more substituents chosenfrom hydroxyl, C₃ to C₈ cycloalkane, C₁ to C₃ hydroxyalkyl and C₁ to C₆alkylamine groups,

g) polyorganosiloxane chains of formula:

in which R¹, R², R³, R⁴, T and m are as defined above, and

h) polyorganosiloxane chains of formula:

The polyorganosiloxanes of the second family may be polymers comprisingat least one moiety corresponding to formula (II):

in which

R¹ and R³, which may be identical or different, are as defined above forformula (I),

R⁷ represents a group as defined above for R¹ and R³, or represents agroup of formula -X-G-R⁹ in which X and G are as defined above forformula (I) and R⁹ represents a hydrogen atom or a linear, branched orcyclic, saturated or unsaturated, C₁ to C₅₀ hydrocarbon-based groupoptionally comprising in its chain one or more atoms chosen from O, Sand N, optionally substituted with one or more fluorine atoms and/or oneor more hydroxyl groups, or a phenyl group optionally substituted withone or more C₁ to C₄ alkyl groups,

R⁸ represents a group of formula -X-G-R⁹ in which X, G and R⁹ are asdefined above,

m₁ is an integer of at least one ranging from 1 to 35,000, for example,from 1 to10,000 and 1 to 2,500, from 1 to 700, and from 6 to 200,including all values and subranges there between; and

m₂ is an integer of at least one ranging from 1 to 35,000, for example,from 1 to10,000 and 1 to 2,500, from 1 to 700, and from 6 to 200,including all values and subranges there between.

According to the invention, the polyorganosiloxane containing polymermay be a homopolymer, that is to say a polymer comprising severalidentical moieties, in particular moieties of formula (I) or of formula(II).

According to the invention, it is also possible to use a polymerconsisting of a copolymer comprising several different moieties offormula (I), that is to say a polymer in which at least one of thegroups R¹, R², R³, R⁴, X, G, Y, m and n is different in one of themoieties. The copolymer may also be formed from several moieties offormula (II), in which at least one of the groups R¹, R³, R⁷, R⁸, m₁ andm₂ is different in at least one of the moieties.

It is also possible to use a copolymer comprising at least one moiety offormula (I) and at least one moiety of formula (II), the moieties offormula (I) and the moieties of formula (II) possibly being identical toor different from each other.

According to preferred embodiments, it is also possible to use acopolymer comprising at least one hydrocarbon-based moiety comprisingtwo groups capable of establishing hydrogen interactions, chosen fromester, amide, sulphonamide, carbamate, thiocarbamate, urea and thioureagroups, and combinations thereof.

These copolymers may be block copolymers or grafted copolymers.

According to a first embodiment of the invention, the groups capable ofestablishing hydrogen interactions are amide groups of formulae —C(O)NH—and —HN—C(O)—.

In this case, the polymer may comprise at least one moiety of formula(III) or (IV):

in which R¹, R², R³, R⁴, X, Y, m and n are as defined above.

Such a moiety may be obtained:

either by a condensation reaction between a silicone containing□,ω-carboxylic acid ends and one or more diamines, according to thefollowing reaction scheme:

or by reaction of two molecules of □-unsaturated carboxylic acid with adiamine according to the following reaction scheme:

CH₂═CH—X¹—COOH+H₂N—Y—NH₂→CH₂═CH—X¹—CO—NH—Y—NH—CO—X¹—CH═CH₂

followed by the addition of a siloxane to the ethylenic unsaturations,according to the following scheme:

in which X¹—(CH₂)₂— corresponds to X defined above and Y, R¹, R², R³, R⁴and m are as defined above;

or by reaction of a silicone containing ε,ω-NH₂ ends and a diacid offormula HOOC—Y—COOH according to the following reaction scheme:

In these polyamides of formula (III) or (IV), m is an integer of atleast one as defined above, and preferably in the range from 1 to 700,for example, from 15 to 500 and from 15 to 45, including all values andsubranges there between; and n is in particular in the range from 1 to500, for example, from 1 to 100 and from 4 to 25, including all valuesand subranges there between; X is preferably a linear or branchedalkylene chain containing from 1 to 30 carbon atoms and in particular 3to 10 carbon atoms, and Y is preferably an alkylene chain that is linearor branched or that possibly comprises rings and/or unsaturations,containing from 1 to 40 carbon atoms, including from 1 to 20 carbonatoms and from 2 to 6 carbon atoms, including all values and subrangesthere between, for example, 6 carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y canoptionally contain in its alkylene portion at least one of the followingelements:

1) 1 to 5 amide, urea or carbamate groups,

2) a C₅ or C₆ cycloalkyl group, and

3) a phenylene group optionally substituted with 1 to 3 identical ordifferent C₁ to C₃ alkyl groups.

In formulae (III) and (IV), the alkylene groups may also be substitutedwith at least one element chosen from the group consisting of:

a hydroxyl group,

a C₃ to C₈ cycloalkyl group,

one to three C₁ to C₄₀ alkyl groups,

a phenyl group optionally substituted with one to three C₁ to C₃ alkylgroups,

a C₁ to C₃ hydroxyalkyl group, and

a C₁ to C₆ aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:

in which R⁵ represents a polyorganosiloxane chain and T represents agroup of formula:

in which a, b and c are, independently, integers ranging from 1 to 10,and R¹⁰ is a hydrogen atom or a group such as those defined for R¹, R²,R³ and R⁴.

In formulae (III) and (IV), R¹, R², R³ and R⁴ preferably represent,independently, a linear or branched C₁ to C₄₀ alkyl group, preferably aCH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or aphenyl group optionally substituted with one to three methyl or ethylgroups.

As has been seen previously, the polymer may comprise identical ordifferent moieties of formula (III) or (IV).

Thus, the polymer may be a polyamide containing several moieties offormula (III) or (IV) of different lengths, i.e. a polyamidecorresponding to the formula:

in which X, Y, n and R¹ to R⁴ have the meanings given above, m₁ and m₂,which are different, are as defined above, and preferably are chosen inthe range from 1 to 1 000, and p is at least one for example rangingfrom 2 to 500 and preferably from 2 to 200.

In this formula, the moieties may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer. In thiscopolymer, the moieties may be not only of different lengths, but alsoof different chemical structures, for example containing differentgroups Y. In this case, the copolymer may correspond to the formula:

in which R¹ to R⁴, X, Y, m₁, m₂, n and p have the meanings given aboveand Y¹ is different from Y but chosen from the groups defined for Y. Aspreviously discussed, the various moieties may be structured to formeither a block copolymer, or a random copolymer or an alternatingcopolymer.

In an embodiment of the invention, the polyorganosiloxane-containingpolymer may also contain a grafted copolymer. Thus, the polyamidecontaining silicone units may be grafted and optionally crosslinked withsilicone chains containing amide groups. Such polymers may besynthesized with trifunctional amines.

In this case, the copolymer may comprise at least one moiety of formula:

in which X¹ and X², which may be identical or different, have themeaning given for X in formula (I), n is as defined in formula (I), Yand T are as defined in formula (I), R¹¹ to R¹⁸ are groups chosen fromthe same group as R¹ to R⁴, m₁ and m₂ are numbers in the range from 1 to1,000, and p is an integer of at least one, for example, p can rangefrom 2 to 500.

In formula (VII), it is preferred that:

p is in the range from 1 to 25, including from 1 to 7, including allvalues and subranges there between,

R¹¹ to R¹⁸ are methyl groups,

T corresponds to one of the following formulae:

in which R¹⁹ is a hydrogen atom or a group chosen from the groupsdefined for R¹ to R⁴, and R²⁰, R²¹ and R²² are, independently, linear orbranched alkylene groups, and more preferably corresponds to theformula:

in particular with R²⁰, R²¹ and R²² representing —CH₂—CH₂—,

m₁ and m₂ are in the range from 15 to 500, including from 15 to 45 andincluding all values and subranges there between,

X¹ and X² represent —(CH₂)₁₀—, and

Y represents —CH₂—.

These polyamides containing a grafted silicone moiety of formula (VII)may be copolymerized with polyamide-silicones of formula (II) to formblock copolymers, alternating copolymers or random copolymers. Theweight percentage of grafted silicone moieties (VII) in the copolymermay range from 0.5% to 30% by weight.

According to the invention, as has been seen previously, the siloxaneunits may be in the main chain or backbone of the polymer, but they mayalso be present in grafted or pendent chains. In the main chain, thesiloxane units may be in the form of segments as described above. In thependent or grafted chains, the siloxane units may appear individually orin segments.

According to the invention, the preferred siloxane-based polyamides are:

polyamides of formula (III) in which m is from 15 to 300, for example,15 to 100, including all values and subranges there between;

mixtures of two or more polyamides in which at least one polyamide has avalue of m in the range from 15 to 50, including all values andsubranges there between and at least one polyamide has a value of m inthe range from 30 to 300, including all values and subranges therebetween;

polymers of formula (V) with m₁ chosen in the range from 15 to 50 and m₂chosen in the range from 30 to 500 with the portion corresponding to m₁representing 1% to 99% by weight of the total weight of the polyamideand the corresponding portion m₂ representing 1% to 99% by weight of thetotal weight of the polyamide;

mixtures of polyamide of formula (III) combining

1) 80% to 99% by weight of a polyamide in which n is equal to 2 to 10and in particular 3 to 6, and

2) 1% to 20% of a polyamide in which n is in the range from 5 to 500 andin particular from 6 to 100;

polyamides corresponding to formula (VI) in which at least one of thegroups Y and Y¹ contains at least one hydroxyl substituent;

polyamides of formula (III) synthesized with at least one portion of anactivated diacid (diacid chloride, dianhydride or diester) instead ofthe diacid;

polyamides of formula (III) in which X represents —(CH₂)₃— or —(CH₂)₁₀;and

polyamides of formula (III) in which the polyamides end with amonofunctional chain chosen from the group consisting of monofunctionalamines, monofunctional acids, monofunctional alcohols, including fattyacids, fatty alcohols and fatty amines, such as, for example,octylamine, octanol, stearic acid and stearyl alcohol.

According to the invention, the end groups of the polymer chain may endwith:

a C₁ to C₅₀ alkyl ester group by introducing a C₁ to C₅₀ monoalcoholduring the synthesis,

a C₁ to C₅₀ alkylamide group by taking as stopping group a monoacid ifthe silicone is □,ω-diaminated, or a monoamine if the silicone is an□,ω-dicarboxylic acid.

According to one embodiment of the invention, it is possible to use acopolymer of silicone polyamide and of hydrocarbon-based polyamide, i.e.a copolymer comprising moieties of formula (III) or (IV) andhydrocarbon-based polyamide moieties. In this case, thepolyamide-silicone moieties may be arranged at the ends of thehydrocarbon-based polyamide.

Polyamide-based polymers containing silicones may be produced by silylicamidation of polyamides based on fatty acid dimer. This approachinvolves the reaction of free acid sites existing on a polyamide as endsites, with organosiloxane-monoamines and/or organosiloxane-diamines(amidation reaction), or alternatively with oligosiloxane alcohols oroligosiloxane diols (esterification reaction). The esterificationreaction requires the presence of acid catalysts, as is known in theart. It is desirable for the polyamide containing free acid sites, usedfor the amidation or esterification reaction, to have a relatively highnumber of acid end groups (for example polyamides with high acidnumbers, for example from 15 to 20).

For the amidation of the free acid sites of the hydrocarbon-basedpolyamides, siloxane diamines with 1 to 300, more particularly 2 to 50and for example, 2, 6, 9.5, 12, 13.5, 23 or 31 siloxane groups, may beused for the reaction with hydrocarbon-based polyamides based on fattyacid dimers. Siloxane diamines containing 13.5 siloxane groups arepreferred, and the best results are obtained with the siloxane diaminecontaining 13.5 siloxane groups and polyamides containing high numbersof carboxylic acid end groups.

The reactions may be carried out in xylene to extract the water producedfrom the solution by azeotropic distillation, or at higher temperatures(about 180 to 200° C.) without solvent. Typically, the efficacy of theamidation and the reaction rates decrease when the siloxane diamine islonger, that is to say when the number of siloxane groups is higher.Free amine sites may be blocked after the initial amidation reaction ofthe diaminosiloxanes by reacting them either with a siloxane acid, orwith an organic acid such as benzoic acid.

For the esterification of the free acid sites on the polyamides, thismay be performed in boiling xylene with about 1% by weight, relative tothe total weight of the reagents, of para-toluenesulphonic acid ascatalyst.

These reactions carried out on the carboxylic acid end groups of thepolyamide lead to the incorporation of silicone moieties only at theends of the polymer chain.

It is also possible to prepare a copolymer of polyamide-silicone, usinga polyamide containing free amine groups, by amidation reaction with asiloxane containing an acid group.

It is also possible to prepare a gelling agent based on a copolymerbetween a hydrocarbon-based polyamide and a silicone polyamide, bytransamidation of a polyamide having, for example, an ethylene-diamineconstituent, with an oligosiloxane-□,ω-diamine, at high temperature (forexample 200 to 300° C.), to carry out a transamidation such that theethylenediamine component of the original polyamide is replaced with theoligosiloxane diamine.

The copolymer of hydrocarbon-based polyamide and of polyamide-siliconemay also be a grafted copolymer comprising a hydrocarbon-based polyamidebackbone with pendent oligosiloxane groups.

This may be obtained, for example:

by hydrosilylation of unsaturated bonds in polyamides based on fattyacid dimers;

by silylation of the amide groups of a polyamide; or

by silylation of unsaturated polyamides by means of an oxidation, thatis to say by oxidizing the unsaturated groups into alcohols or diols, toform hydroxyl groups that are reacted with siloxane carboxylic acids orsiloxane alcohols. The olefinic sites of the unsaturated polyamides mayalso be epoxidized and the epoxy groups may then be reacted withsiloxane amines or siloxane alcohols.

The polyorganosiloxane containing polymers used in the composition ofthe invention are most preferably polymers of the polyorganosiloxanetype such as those described in documents U.S. Pat. No. 5,874,069, U.S.Pat. No. 5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680,the entire disclosures of which are hereby incorporated by reference.

According to another embodiment of the invention, the polyorganoxiloxanecontaining polymer is a homopolymer or a copolymer comprising urethaneor urea groups.

As previously discussed, the polymer may comprise polyorganosiloxanemoieties containing two or more urethane and/or urea groups, either inthe backbone of the polymer or on side chains or as pendent groups.

The polymers comprising at least two urethane and/or urea groups in thebackbone may be polymers comprising at least one moiety corresponding tothe following formula:

in which R¹, R², R³, R⁴, X, Y, m and n have the meanings given above forformula (I), and U represents —O— or —NH—, such that:

corresponds to a urethane or urea group.

In this formula (VIII), Y may be a linear or branched C₁ to C₄₀ alkylenegroup, optionally substituted with a C₁ to C₁₅ alkyl group or a C₅ toC₁₀ aryl group. Preferably, a —(CH₂)₆— group is used.

Y may also represent a C₅ to C₁₂ cycloaliphatic or aromatic group thatmay be substituted with a C₁ to C₁₅ alkyl group or a C₅ to C₁₀ arylgroup, for example a radical chosen from the methylene-4,4-biscyclohexylradical, the radical derived from isophorone diisocyanate, 2,4- and2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4′-biphenylenemethane.Generally, it is preferred for Y to represent a linear or branched C₁ toC₄₀ alkylene radical or a C₄ to C₁₂ cycloalkylene radical.

Y may also represent a polyurethane or polyurea block corresponding tothe condensation of several diisocyanate molecules with one or moremolecules of coupling agents of the diol or diamine type. In this case,Y comprises several urethane or urea groups in the alkylene chain.

It may correspond to the formula:

in which B¹ is a group chosen from the groups given above for Y, U is—O— or —NH— and B² is chosen from:

linear or branched C₁ to C₄₀ alkylene groups, which can optionally bearan ionizable group such as a carboxylic acid or sulphonic acid group, ora neutralizable or quaternizable tertiary amine group,

C₅ to C₁₂ cycloalkylene groups, optionally bearing alkyl substituents,for example one to three methyl or ethyl groups, or alkylene, forexample the diol radical: cyclohexanedimethanol,

phenylene groups that may optionally bear C₁ to 0₃ alkyl substituents,and

groups of formula:

in which T is a hydrocarbon-based trivalent radical possibly containingone or more hetero atoms such as oxygen, sulphur and nitrogen and R⁵ isa polyorganosiloxane chain or a linear or branched C₁ to C₅₀ alkylchain.

T can represent, for example:

with w being an integer ranging from 1 to 10 and R⁵ being apolyorganosiloxane chain.

When Y is a linear or branched C₁ to C₄₀ alkylene group, the —(CH₂)₂—and —(CH₂)₆— groups are preferred.

In the formula given above for Y, d may be an integer ranging from 0 to5, preferably from 0 to 3 and more preferably equal to 1 or 2.

Preferably, B² is a linear or branched C₁ to C₄₀ alkylene group, inparticular —(CH₂)₂— or —(CH₂)₆— or a group:

with R⁵ being a polyorganosiloxane chain.

As previously discussed, the polyorganosiloxane containing polymer maybe formed from silicone urethane and/or silicone urea moieties ofdifferent length and/or constitution, and may be in the form of block orrandom copolymers.

According to the invention, the silicone may also comprise urethaneand/or urea groups no longer in the backbone but as side branches.

In this case, the polymer may comprise at least one moiety of formula:

in which R¹, R², R³, m₁ and m₂ have the meanings given above for formula(I),

U represents O or NH,

R²³ represents a C₁ to C₄₀ alkylene group, optionally comprising one ormore hetero atoms chosen from O and N, or a phenylene group, and

R²⁴ is chosen from linear, branched or cyclic, saturated or unsaturatedC₁ to C₅₀ alkyl groups, and phenyl groups optionally substituted withone to three C₁ to C₃ alkyl groups.

The polymers comprising at least one moiety of formula (X) containsiloxane units and urea or urethane groups, and they may be used, forexample, as gelling agents in the compositions of the invention.

The siloxane polymers may have a single urea or urethane group bybranching or may have branches containing two urea or urethane groups,or alternatively they may contain a mixture of branches containing oneurea or urethane group and branches containing two urea or urethanegroups.

They may be obtained from branched polysiloxanes, comprising one or twoamino groups by branching, by reacting these polysiloxanes withmonoisocyanates.

As examples of starting polymers of this type containing amino anddiamino branches, mention may be made of the polymers corresponding tothe following formulae:

In these formulae, the symbol “/” indicates that the segments may be ofdifferent lengths and in a random order, and R represents a linearaliphatic group preferably containing 1 to 6 carbon atoms, including 1to 3 carbon atoms.

Such polymers containing branching may be formed by reacting a siloxanepolymer, containing at least three amino groups per polymer molecule,with a compound containing only one monofunctional group (for example anacid, an isocyanate or an isothiocyanate) to react this monofunctionalgroup with one of the amino groups and to form groups capable ofestablishing hydrogen interactions. The amino groups may be on sidechains extending from the main chain of the siloxane polymer, such thatthe groups capable of establishing hydrogen interactions are formed onthese side chains, or alternatively the amino groups may be at the endsof the main chain, such that the groups capable of hydrogen interactionwill be end groups of the polymer.

As a procedure for forming a polymer containing siloxane units andgroups capable of establishing hydrogen interactions, mention may bemade of the reaction of a siloxane diamine and of a diisocyanate in asilicone solvent so as to provide a gel directly. The reaction may beperformed in a silicone fluid, the resulting product being dissolved inthe silicone fluid, at high temperature, the temperature of the systemthen being reduced to form the gel.

The polymers that are preferred for incorporation into the compositionsaccording to the present invention are siloxane-urea copolymers that arelinear and that contain urea groups as groups capable of establishinghydrogen interactions in the backbone of the polymer.

As an illustration of a polysiloxane ending with four urea groups,mention may be made of the polymer of formula:

in which Ph is a phenyl group and n is a number larger than 0, whichincludes, at least 1, 2 to 500, 2 to 200, from 1 to 300, in particularfrom 1 to 100, and all values and subranges there between, for example50.

This polymer is obtained by reacting the following polysiloxanecontaining amino groups:

with phenyl isocyanate.

The polymers of formula (VIII) comprising urea or urethane groups in thechain of the silicone polymer may be obtained by reaction between asilicone containing □,ω-NH₂ or —OH end groups, of formula:

in which m, R¹, R², R³, R⁴ and X are as defined for formula (I) and adiisocyanate OCN—Y—NCO in which Y has the meaning given in formula (I);and optionally a diol or diamine coupling agent of formula H₂N—B²—NH₂ orHO—B²—OH, in which B² is as defined in formula (IX).

According to the stoichiometric proportions between the two reagents,diisocyanate and coupling agent, Y may have the formula (IX) with dequal to 0 or d equal to 1 to 5.

As in the case of the polyamide silicones of formula (II) or (III), itis possible to use in the invention polyurethane or polyurea siliconescontaining moieties of different length and structure, in particularmoieties whose lengths differ by the number of silicone units. In thiscase, the copolymer may correspond, for example, to the formula:

in which R¹, R², R³, R⁴, X, Y and U are as defined for formula (VIII)and m₁, m₂, n and p are as defined for formula (V).

Branched polyurethane or polyurea silicones may also be obtained using,instead of the diisocyanate OCN—Y—NCO, a triisocyanate of formula:

A polyurethane or polyurea silicone containing branches comprising anorganosiloxane chain with groups capable of establishing hydrogeninteractions is thus obtained. Such a polymer comprises, for example, amoiety corresponding to the formula:

in which X¹ and X², which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R¹¹ to R¹⁸ are groups chosen from the samegroup as R¹ to R⁴, m₁ and m₂ are as defined above.

As in the case of the polyamides, this copolymer can also comprisepolyurethane silicone moieties without branching.

In another embodiment of the invention, the siloxane-based polyureas andpolyurethanes that are preferred are:

polymers of formula (VIII) in which m is from 15 to 300, for example, 15to 100 and all values and subranges there between;

mixtures of two or more polymers in which at least one polymer has avalue of m in the range from 15 to 50 and at least one polymer has avalue of m in the range from 30 to 300, including all values andsubranges there between;

polymers of formula (XII) with m₁ chosen in the range from 15 to 50 andm₂ chosen in the range from 30 to 500 with the portion corresponding tom₁ representing 1% to 99% by weight of the total weight of the polymerand the portion corresponding to m₂ representing 1% to 99% by weight ofthe total weight of the polymer;

mixtures of polymer of formula (VIII) combining

1) 80% to 99% by weight of a polymer in which n is equal to 2 to 10 andin particular 3 to 6, and

2) 1% to 20% of a polymer in which n is in the range from 5 to 500 andin particular from 6 to 100,

copolymers comprising two moieties of formula (VIII) in which at leastone of the groups Y contains at least one hydroxyl substituent;

polymers of formula (VIII) synthesized with at least one portion of anactivated diacid (diacid chloride, dianhydride or diester) instead ofthe diacid;

polymers of formula (VIII) in which X represents —(CH₂)₃— or —(CH₂)₁₀—;and

polymers of formula (VIII) in which the polymers end with amultifunctional chain chosen from the group consisting of monofunctionalamines, monofunctional acids, monofunctional alcohols, including fattyacids, fatty alcohols and fatty amines, such as, for example,octylamine, octanol, stearic acid and stearyl alcohol.

As in the case of the polyamides, copolymers of polyurethane or polyureasilicone and of hydrocarbon-based polyurethane or polyurea may be usedin the invention by performing the reaction for synthesizing the polymerin the presence of an □,ω-difunctional block of non-silicone nature, forexample a polyester, a polyether or a polyolefin.

As has been seen previously, homopolymers or copolymers of the inventionmay contain siloxane moieties in the main chain of the polymer andgroups capable of establishing hydrogen interactions, either in the mainchain of the polymer or at the ends thereof, or on side chains orbranches of the main chain. This may correspond to the following fivearrangements:

in which the continuous line is the main chain of the siloxane polymerand the squares represent the groups capable of establishing hydrogeninteractions.

In case (1), the groups capable of establishing hydrogen interactionsare arranged at the ends of the main chain.

In case (2), two groups capable of establishing hydrogen interactionsare arranged at each of the ends of the main chain.

In case (3), the groups capable of establishing hydrogen interactionsare arranged within the main chain in repeating moieties.

In cases (4) and (5), these are copolymers in which the groups capableof establishing hydrogen interactions are arranged on branches of themain chain of a first series of moieties that are copolymerized withmoieties not comprising groups capable of establishing hydrogeninteractions. Preferably, the values n, x and y are such that thepolymer has the desired properties in terms of an agent for gellingfatty phases, preferably fatty phases based on silicone oil.

As examples of polymers that may be used, mention may be made of thesilicone polyamides obtained in accordance with the disclosure in U.S.Pat. No. 5,981,680, the entire disclosure of which is herebyincorporated by reference.

Further examples of polyorganosiloxane containing polymers are set forthin U.S. Pat. Nos. 6,503,632 and 6,569,955, both of which are herebyincorporated by reference in their entirety.

As noted above, the polymers of the present invention can be solid orliquid at room temperature. When solid, the polymers preferably have asoftening point from 50 to 130° C. Most preferably, they have asoftening point ranging from 65 to 150° C., including from 70° C. to130° C. This softening point is lower than that of other structuringpolymers, which facilitates the use of the polymers that are the subjectof the invention, and limits the deteriorations of the liquid fattyphase.

As noted above, the polyorganosiloxane containing polymers of thepresent invention contain both siloxane units and at least two groupscapable of establishing hydrogen interactions such as amide linkages.The siloxane units can provide compatibility with a silicone fluid, ifpresent, (for example with the cyclomethicones), while the groupscapable of establishing hydrogen interactions and the spacing andselection of the locations of the amide linkages can facilitate gelationand the formation of cosmetic products.

According to preferred embodiments, the polyorganosiloxane-containingpolymer is present in the composition in an amount effective to providetransfer resistant properties to the composition. Preferably, thepolyorganosiloxane-containing polymer also provides at least one of thefollowing properties to the composition: pliability, softness, wearingcomfort, flexibility, adherence and non-tackiness.

In the compositions, the polyorganosiloxane-containing polymers arepreferably present in an amount of 0.1-80 percent by weight, morepreferably from 0.5 to 30 percent by weight, even more preferably from 5to 25 percent by weight and most preferably from 10 to 20 percent byweight of the total weight of the composition. One of ordinary skill inthe art will recognize that the polyorganosiloxane-containing polymermay be commercially available, and may come from suppliers in the formof a dilute solution. In such case, the amounts of thepolyorganosiloxane-containing polymer disclosed herein therefore reflectthe weight percent of active material. All numerical ranges andsubranges are included within the numerical ranges identified above.

Volatile Non-Silicone Oil

According to preferred embodiments of the present invention, thecomposition comprises at least one volatile non-silicone oil. Anysuitable volatile non-silicone oil can be used. The volatility of theoils can be determined using the evaporation speed as set forth in U.S.Pat. No. 6,338,839, hereby incorporated by reference.

According to preferred embodiments, suitable volatile non-silicone oilsinclude but are not limited to volatile hydrocarbon oils, volatilealcohols, volatile esters and volatile ethers. Examples of such volatilenon-silicone oils include, but are not limited to, volatile hydrocarbonoils having from 8 to 16 carbon atoms and their mixtures and inparticular branched C₈ to C₁₆ alkanes such as C₈ to C₁₆ isoalkanes (alsoknown as isoparaffins), isododecane, isodecane, isohexadecane, and forexample, the oils sold under the trade names of Isopar or Permethyl, theC₈ to C₁₆ branched esters such as isohexyl or isodecyl neopentanoate andtheir mixtures. Preferably, the volatile non-silicone oils have a flashpoint of at least 40° C.

Non-limiting examples of volatile non-silicone volatile oils are givenin Table 1 below.

TABLE 1 Compound Flash Point (° C.) Isododecane 43 Isohexadecane 102Isodecyl Neopentanoate 118 Propylene glycol n-butyl ether 60 Ethyl3-ethoxypropionate 58 Propylene glycol methylether acetate 46 Isopar L(isoparaffin C₁₁-C₁₃) 62 Isopar H (isoparaffin C₁₁-C₁₂) 56

In the compositions, the volatile non-silicone oil is preferably presentin an amount of about 0.1-80 percent by weight, more preferably fromabout 5 to about 60 percent by weight, even more preferably from 7 toabout 50 percent by weight and most preferably from about 10 to about 40percent by weight of the total weight of the composition. All numericalranges and subranges are included within the numerical ranges identifiedabove.

Alkylene Polymer Wax

According to preferred embodiments of the present invention, thecomposition comprises an alkylene polymer wax such as, for example, anethylene polymer wax, a butylene polymer wax, a propylene polymer wax,etc. The alkylene polymer wax is preferably an ethylene homopolymer wax.

Preferably, the ethylene homopolymer wax has an average molecular weightof between about 200 and about 700, more preferably between about 400and about 500, as determined by vapor pressure osmometry. Mostpreferably, the ethylene homopolymer wax has a melting temperature rangefrom about 82° C. to about 91° C.

In the compositions, the alkylene polymer wax is preferably present inan amount of about 1.0 to about 30 percent by weight, more preferablyfrom about 1.0 to about 20 percent by weight, even more preferably fromabout 1.0 to about 10 percent by weight of the total weight of thecomposition. All numerical ranges and subranges are included within thenumerical ranges identified above.

According to particularly preferred embodiments, the compositionscomprise at least two alkylene polymer waxes. In the embodiment wheretwo alkylene polymer waxes are present, the weight ratio of the lowermolecular weight wax (for example, PE 400) to the higher molecularweight wax (for example, PE 500) is preferably between about 30:70 toabout 99:1 (weight fraction of about 0.3 to about 1.0), with the ratioof about 30:70 to about 80:20 being most preferred (weight fraction ofabout 0.3 to about 0.80).

Suitable ethylene homopolymers include but are not limited to those soldunder the trade names “Performalene 400 (“PE 400”)” and “Performalene500 (“PE 500”),” those sold under the trade names “Polywax 500”,“Polywax 655”, and “Polywax 1.000” by Bareco, those sold under the tradenames “PE 1.500 F” and PEW 1.555” by Langer & Co., those commercializedunder the trade name “TN Wax 1.495” sold by R. T. Newey, and “AC 1702”sold by Allied Chemical. “Polywax 500”, “Polywax 655”, and “Polywax1,000” are homopolymers of ethylene having molecular weights of 500,700, and 1,000, respectively, as determined by vapor pressure osmometry.

Suitable ethylene copolymers include but are not limited toethylene-propylene copolymers sold under the trade names “PetroliteCP-7” and “Petrolite CP-12” sold by Bareco, and the ethylene-hexenecopolymers sold under the trade names “Petrolite CH-7” and “PetroliteCH-12” by Bareco. Preferably, the ethylene copolymer wax has an averagemolecular weight of between about 200 and about 1000, more preferablybetween about 400 and about 700, and most preferably between about 500and about 700. Most preferably, the ethylene copolymer wax has a meltingtemperature range from about 82° C. to about 91° C.

Preferably, the total amount of wax present in the compositions of thepresent invention, including but not limited to alkylene polymer waxesand long-chain alcohol waxes (if present), is 50% or less based on thetotal weight of the composition, with between about 10% and about 50%being preferred, and between about 10% and about 20% being mostpreferred.

Silicone Film Forming Agents

According to preferred embodiments, the composition comprises one ormore silicone film forming agents. Preferably, the at least one siliconefilm forming agent is a silicone resin film forming agent such as an MKor an MQ resin, or mixtures thereof.

Silicone resin nomenclature is known in the art as “MDTQ” nomenclature,whereby a silicone resin is described according to the various monomericsiloxane units which make up the polymer.

Each letter of “MDTQ” denotes a different type of unit. The letter Mdenotes the monofunctional unit (CH₃)₃SiO_(1/2). This unit is consideredto be monofunctional because the silicone atom only shares one oxygenwhen the unit is part of a polymer. The “M” unit can be represented bythe following structure:

At least one of the methyl groups of the M unit may be replaced byanother group, e.g., to give a unit with formula [R(CH₃)₂]SiO_(1/2), asrepresented in the following structure:

wherein R is chosen from groups other than methyl groups. Non-limitingexamples of such groups other than methyl groups include alkyl groupsother than methyl groups, alkene groups, alkyne groups, hydroxyl groups,thiol groups, ester groups, acid groups, ether groups, wherein thegroups other than methyl groups may be further substituted.

The symbol D denotes the difunctional unit (CH₃)₂SiO_(2/2) wherein twooxygen atoms bonded to the silicone atom are used for binding to therest of the polymer. The “D” unit, which is the major building block ofdimethicone oils, can be represented as:

At least one of the methyl groups of the D unit may be replaced byanother group, e.g., to give a unit with formula [R(CH₃)₂]SiO_(1/2).

The symbol T denotes the trifunctional unit, (CH₃)SiO_(3/2) and can berepresented as:

At least one of the methyl groups of the T unit may be replaced byanother group, e.g., to give a unit with formula [R(CH₃)₂]SiO_(1/2).

Similarly, the symbol Q denotes the tetrafunctional unit, SiO_(4/2)wherein all four oxygens bonded to the silicone atom are bonded to therest of the polymer.

Thus, a vast number of different silicone polymers can be manufactured.Further, it would be clear to one skilled in the art that the propertiesof each of the potential silicone polymers will vary depending on thetype(s) of monomer(s), the type(s) of substitution(s), the size of thepolymeric chain, the degree of cross linking, and size of any sidechain(s).

Non-limiting examples of silicone polymers include silanes, siloxanes,siloxysilicates, and silsesquioxanes. A non-limiting example of such asiloxane is polydimethylsiloxane (PDMS). Polydimethylsiloxanes aregenerally composed of long straight chains of (CH₃)₂SiO_(2/2) (i.e., Dunits) and have viscosities which are dependent on both the size of thepolymer and the presence and nature of any substituent(s) on thepolymer. A non-limiting example of a siloxysilicate istrimethylsiloxysilicate, which may be represented by the followingformula:

[(CH₃)₃—Si—O]_(x)—(SiO_(4/2))_(y)

(i.e, MQ units) wherein x and y may, for example, range from 50 to 80.Silsesquioxanes, on the other hand, may be represented by the followingformula:

(CH₃SiO_(3/2))_(.x)

(i.e., T Units) wherein x may, for example, have a value of up toseveral thousand.

Polymethylsilsesquioxanes are silsesquioxanes that do not have asubstituent replacing the methyl groups. Certainpolymethylsilsesquioxanes have previously been used in hair carecompositions. See, e.g., U.S. Pat. No. 5,246,694, the disclosure ofwhich is incorporated herein by reference, which discloses a shampoocomposition comprising a surfactant, an aqueous emulsion of highlyviscous silicone in volatile silicone and a cationic polymer which is aderivative of guar gum. The highly viscous silicone disclosed thereinmay be chosen from silicone resins including a polymethylsilsesquioxanesuch as Resin MK (also called SiliconHarz MK) which is available fromWacker, and a siloxysilicate such as Resin MQ which is available fromGeneral Electric and Dow Corning.

The Resin MK and Resin MQ silicone resins may form a film after avolatile carrier has evaporated. The MQ film is generally hard andbrittle at room temperature, while the MK film is generally continuousand flexible, i.e., not brittle. Depending on the application,plasticizers may be added to help obtain a more flexible, thus morecomfortable, film.

In one embodiment, the silicone film former may be apolymethylsilsesquioxane film former such as Belsil PMS MK, alsoreferred to as Resin MK, available from Wacker Chemie. Thispolymethylsilsesquioxane film former is a polymer comprising polymerizedrepeating units of CH₃SiO_(3/2) (T units) and may also contain up to 1%by weight or by mole of units of the formula (CH₃)₂SiO_(2/2) (D units).The weight-average molecular weight of this polymer has been estimatedto be 10,000. It is believed that the polymers are in a “cage” and“ladder” configuration, as exemplified in the figures below. Themajority of the polymer is in the “ladder” configuration, wherein theends of the polymer are capped with ethoxy (CH₃CH₂O) groups. The ethoxygroups are generally present in an amount of 4.5% by weight and the molepercent is generally 7% (silicone units). As ethoxy groups may reactwith water, a small and variable amount of SiOH may also be present inthe polymer.

Another non-limiting example of the at least onepolymethylsilsesquioxane film former suitable for use in the presentinvention is KR-220L, which is available from SHIN-ETSU. Thispolymethylsilsesquioxane film former is composed of silicone T-units(i.e., those of formula CH₃SiO_(3/2)) and has Si—OH (or silanol) endunits. There are no D units in KR-220L.

Other non-limiting examples of the at least one polymethylsilsesquioxanefilm former that may be useful in the practice of the invention includeKR-242A (which is comprised of methyl T units (98%) and dimethyl D units(2%) and has Si—OH end units) and KR-251 (which is comprised of methyl Tunits (88%) and dimethyl D units (12%) and has Si—OH end units), both ofwhich are available from SHIN-ETSU.

Depending on the application, the concentration of the at least onepolymethylsilsesquioxane film former in the presently claimedcomposition may vary considerably. One of skill in the art will be ableto determine routinely the amount of the at least onepolymethylsilsesquioxane film former depending on the desiredapplication.

In another embodiment, the silicone film former may be chosen fromsiloxysilicates. Preferably, the siloxysilicate istrimethylsiloxysilicate, which may or may not be in powder form.Trimethylsiloxysilicate (TMS) is commercially available from GeneralElectric under the tradename SR1000 and from Wacker under the tradenameTMS 803. TMS is also commercially available from Dow Chemical in asolvent, such as for example, cyclomethicone. However, according to thepresent invention, TMS may be used in the form of 100% active material,that is, not in a solvent.

Further non-limiting examples of the silicone film formers includesilicone/(meth)acrylate copolymers, such as those as described in U.S.Pat. Nos. 5,061,481, 5,219,560, and 5,262,087, the disclosures of whichare hereby incorporated by reference. Still further non-limitingexamples of silicone film formers are non-polar silicone copolymerscomprising repeating units of at least one polar (meth)acrylate unit andvinyl copolymers grafted with at least one non-polar silicone chain.Non-limiting examples of such copolymers are acrylates/dimethiconecopolymers such as those commercially available from Shin-Etsu, forexample, the product sold under the tradename KP-545, oracrylates/stearyl acrylate/dimethicone acrylates copolymers, such asthose commercially available from Shin-Etsu, for example, the productsold under the tradename KP-561, and acrylates/behenylacrylate/dimethicone acrylates copolymer, such as those commerciallyavailable from Shin-Etsu, for example, the product sold under thetradename KP-562.

Other non-limiting examples of silicone film formers suitable for use inthe present invention are silicone esters comprising units of formulae(XIV) and (XV), disclosed in U.S. Pat. Nos. 6,045,782, 5,334,737, and4,725,658, the disclosures of which are hereby incorporated byreference:

R_(a)R^(E) _(b)SiO_([4-(a+b)/2])  (XIV); and

R′_(x)R^(E) _(y)SiO_(1/2)   (XV)

wherein

R and R′, which may be identical or different, are each chosen fromoptionally substituted hydrocarbon groups;

a and b, which may be identical or different, are each a number rangingfrom 0 to 3, with the proviso that the sum of a and b is a numberranging from 1 to 3,

x and y, which may be identical or different, are each a number rangingfrom 0 to 3, with the proviso that the sum of x and y is a numberranging from 1 to 3;

R^(E), which may be identical or different, are each chosen from groupscomprising at least one carboxylic ester.

In one embodiment, R^(E) groups are chosen from groups comprising atleast one ester group formed from the reaction of at least one acid andat least one alcohol. In another embodiment, the at least one acidcomprises at least two carbon atoms. In another embodiment, the at leastone alcohol comprises at least ten carbon atoms. Non-limiting examplesof the at least one acid include branched acids such as isostearic acid,and linear acids such as behenic acid. Non-limiting examples of the atleast one alcohol include monohydric alcohols and polyhydric alcohols,such as n-propanol and branched etheralkanols such as(3,3,3-trimethylolpropoxy)propane.

Further non-limiting examples of the at least one silicone film formerinclude liquid siloxy silicates and silicone esters such as thosedisclosed in U.S. Pat. No. 5,334,737, the disclosure of which is herebyincorporated by reference, such as diisostearoyl trimethylolpropanesiloxysilicate and dilauroyl trimethylolpropane siloxy silicate, whichare commercially available from General Electric under the tradenames SF1318 and SF 1312, respectively.

Yet further non-limiting examples of the at least one silicone filmformer include polymers comprising a backbone chosen from vinylpolymers, methacrylic polymers, and acrylic polymers and at least onechain chosen from pendant siloxane groups and pendant fluorochemicalgroups. Non-limiting examples of such polymers comprise at least oneunit derived from at least one A monomer, at least one unit derived fromat least one C monomer, at least one unit derived from D monomers, and,optionally, at least one unit derived from at least one B monomer,wherein:

A, which may be identical or different, are each chosen fromfree-radically-polymerizable acrylic esters of at least one alcoholchosen from 1,1,-dihydroperfluoroalkanols, omega-hydridofluoroalkanols,fluoroalkylsulfonamido alcohols, cyclic fluoroalkyl alcohols, andfluoroether alcohols, and analogs of any of the foregoing at least onealcohols, and free-radically-polymerizable methacrylic esters of atleast one alcohol chosen from 1,1,-dihydroperfluoroalkanols,omega-hydridofluoroalkanols, fluoroalkylsulfonamido alcohols, cyclicfluoroalkyl alcohols, and fluoroether alcohols, and analogs of any ofthe foregoing at least one alcohols;

B, which may be identical or different, are each chosen from reinforcingmonomers which are copolymerizable with at least one A monomer;

C, which may be identical or different, are each chosen from monomershaving the formula:

X(Y)_(n)Si(R)_(3-m)Z_(m)

wherein

X is chosen from vinyl groups which are copolymerizable with at leastone A monomer and at least one B monomer,

Y is chosen from divalent allylene groups, divalent arylene groups,divalent alkarylene groups, and divalent aralkylene groups, wherein thegroups comprise from 1 to 30 carbon atoms, and further wherein thegroups optionally further comprise at least one group chosen from estergroups, amide groups, urethane groups, and urea groups;

n is zero or 1;

m is a number ranging from 1 to 3;

R, which may be identical or different, are each chosen from hydrogen,C₁-C₄ alkyl groups, aryl groups, and alkoxy groups; and

Z, which may be identical or different, are each chosen from monovalentsiloxane polymeric groups; and

D, which may be identical or different, are each chosen fromfree-radically-polymerizable acrylate copolymers andfree-radically-polymerizable methacrylate copolymers. Such polymers andtheir manufacture are disclosed in U.S. Pat. Nos. 5,209,924 and4,972,037, and WO 01/32737, the disclosures of which are herebyincorporated by reference.

Other non-limiting examples of the at least one silicone film formerinclude silicone/acrylate graft terpolymers, for example, those havingthe formula:

wherein

a, b, and c are present in a weight ratio of 69.9:0.1:30 respectively,

R and R₁, which may be identical or different, are each chosen fromhydrogen and C₁-C₆ alkyl groups; and

m is a number ranging from 100-150.

In an embodiment, m is chosen to provide a macromer having a molecularweight ranging from 8,000 to 12,000, such as 10,000. In anotherembodiment, m is a number ranging from 124-135, such as 130.Non-limiting examples of these copolymers are described in WO 01/32727A1, the disclosure of which is hereby incorporated by reference.

Still other examples of suitable silicone film formers includecopolymers comprising a backbone chosen from vinyl backbones,methacrylic backbones, and acrylic polymeric backbones and furthercomprising at least one pendant siloxane group. Non-limiting examples ofsuch polymers are disclosed in U.S. Pat. Nos. 4,693,935, 4,981,903,4,981,902, the disclosures of which are hereby incorporated byreference.

In an embodiment, the at least one copolymer comprises at least one Amonomer, at least one C monomer, and, optionally at least one B monomer,wherein the at least one A monomer is chosen fromfree-radically-polymerizable vinyl monomers,free-radically-polymerizable methacrylate monomers, andfree-radically-polymerizable acrylate monomers; the at least one Bmonomer, if present, is chosen from at least one reinforcing monomercopolymerizable with the at least one A monomer, and the at least one Cmonomer is chosen from monomers having the formula:

X(Y)_(n)Si(R)_(3-m)Z_(m)

wherein:

X is chosen from vinyl groups which are copolymerizable with the atleast one A monomer and with the at least one B monomer;

Y is chosen from divalent groups;

n is zero or 1;

m is a number ranging from 1 to 3;

R, which may be identical or different, are each chosen from hydrogen,optionally substituted C₁-C₁₀ alkyl groups, optionally substitutedphenyl groups, and optionally substituted C₁-C₁₀ alkoxy groups; and

Z, which may be identical or different, are each chosen from monovalentsiloxane polymeric groups.

Non-limiting examples of A monomers include methacrylic acid esters ofC₁-C₁₂ linear alcohols, methacrylic acid esters of C₁-C₁₂ of branchedalcohols, styrene monomers, vinyl esters, vinyl chloride monomers,vinylidene chloride monomers, and acryloyl monomers.

Non-limiting examples of B monomers include acrylic monomers comprisingat least one group chosen from hydroxyl, amino, and ionic groups, andmethacrylic monomers comprising at least one group chosen from hydroxyl,amino, and ionic groups. Non-limiting examples of ionic groups includequaternary ammonium groups, carboxylate salts, and sulfonic acid salts.

The C monomers are the same as those described for the C monomers in theprevious paragraphs.

Other non-limiting examples of the silicone film-former include acopolymer chosen from vinyl-silicone graft copolymers having thefollowing formula and vinyl-silicone block copolymers having thefollowing formula:

wherein

G₅, which may be identical or different, are each chosen from alkylgroups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups,fluoroalkyl groups, hydrogen, and —ZSA groups, wherein

A is chosen from vinyl polymeric segments comprising at least onepolymerized free-radically-polymerizable monomer, and

Z is chosen from divalent C₁-C₁₀ alkylene groups, divalent aralkylenegroups, divalent arylene groups, and divalent alkoxylalkylene groups. Inan embodiment Z is chosen from methylene groups and propylene groups.

G₆, which may be identical or different, are each chosen from alkylgroups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups,fluoroalkyl groups, hydrogen, and —ZSA groups, as defined above;

G₂ comprises A;

G₄ comprises A;

R₁, which may be identical or different, are each chosen from alkylgroups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups,fluoroalkyl groups, hydrogen, and hydroxyl. In one embodiment, R₁ ischosen from C₁-C₄ alkyl groups, such as methyl groups, and hydroxyl.

R₂, which may be identical or different, are each chosen from divalentC₁₋₁₀ alkylene groups, divalent arylene groups, divalent aralkylenegroups, and divalent alkoxyalkylene groups. In one embodiment, R₂ ischosen from divalent C₁-C₃ alkylene groups and divalent C₇-C₁₀aralkylene groups. In another embodiment, R₂ is chosen from —CH₂— groupsand divalent 1,3-propylene groups.

R₃, which may be identical or different, are each chosen from alkylgroups, aryl groups, aralkyl groups alkoxy groups, alkylamino groups,fluoroalkyl groups, hydrogen, and hydroxyl. In one embodiment, R₃ ischosen from C₁-C₄ alkyl groups and hydroxyl. In another embodiment, R₃is chosen from methyl groups.

R₄, which may be identical or different, are each chosen from divalentC₁-C₁₀ alkylene groups, divalent arylene groups, divalent aralkylenegroups, and divalent alkoxyalkylene groups. In one embodiment, R₄ ischosen from divalent C₁-C₃ alkylene groups and divalent C₇-C₁₀aralkylene groups. In another embodiment, R₄ is chosen from divalent—CH₂— groups and divalent 1,3-propylene groups.

x is a number ranging from 0 to 3;

y is a number greater than or equal to 5. In an embodiment, y rangesfrom 10 to 270, and in another embodiment, y ranges from 40 to 270.

q is a number ranging from 0 to 3;

Non-limiting examples of these polymers are described in U.S. Pat. No.5,468,477, the disclosure of which is hereby incorporated by reference.A non-limiting example of such polymers ispoly(dimethylsiloxane)-g-poly(isobutyl methacrylate), which iscommercially available from 3M Company under the tradename VS 70 IBM.

According to preferred embodiments, the silicone film former is presentin the composition in an amount ranging from 0.1% to 30% by weightrelative to the total weight of the composition. Preferably, thesilicone film former is present in an amount ranging from 0.5% to 20% byweight relative to the total weight of the composition, and morepreferably from 1% to 10%. One of ordinary skill in the art willrecognize that the silicone film former of the present invention may becommercially available, and may come from suppliers in the form of adilute solution. The amounts of the silicone film former disclosedherein therefore reflect the weight percent of active material.

Coloring Agent

The composition of the present invention may optionally contain at leastone coloring agent. According to preferred embodiments of the presentinvention, the composition further comprises at least one coloringagent.

In the composition, any coloring agent can be used. The at least onecoloring agent is preferably chosen from pigments, dyes such asliposoluble dyes, nacreous pigments, and/or pearling agents.

Representative liposoluble dyes which may be used according to thepresent invention include Sudan Red, DC Red 17, DC Green 6, β-carotene,soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5,annatto, and quinoline yellow. The liposoluble dyes, when present,generally have a concentration ranging up to 20% by weight of the totalweight of the composition, most preferably from 0.0001% to 6%.

The nacreous pigments which may be used according to the presentinvention include but are not limited to nacreous pigments such as micacoated with titanium or with bismuth oxychloride, colored nacreouspigments such as titanium mica with iron oxides, titanium mica withferric blue or chromium oxide, titanium mica with an organic pigmentchosen from those mentioned above, and nacreous pigments based onbismuth oxychloride. The nacreous pigments, if present, may be presentin the composition in a concentration ranging up to 50% by weight of thetotal weight of the composition, such as from 0.1% to 20%, preferablyfrom 0.1% to 15%.

The pigments, which may be used according to the present invention, maybe chosen from white, colored, inorganic, organic, polymeric,nonpolymeric, coated and uncoated pigments. Representative examples ofmineral pigments include titanium dioxide, optionally surface-treated,zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides,manganese violet, ultramarine blue, chromium hydrate, and ferric blue.Representative examples of organic pigments include carbon black,pigments of D & C type, and lakes based on cochineal carmine, barium,strontium, calcium, and aluminum.

If present, the pigments may be present in the composition in aconcentration ranging up to 50% by weight of the total weight of thecomposition, such as from 1% to 30%, and further such as from 1% to 15%.

Long-Chain Alcohol Wax

The composition of the present invention may optionally contain at leastone long-chain alcohol wax. According to preferred embodiments of thepresent invention, the composition further comprises at least onelong-chain alcohol wax. It is believed that the long-chain wax helpsimprove, among other things, the hardness of solid compositions.

Preferably, the at least one long-chain alcohol wax has an averagecarbon chain length of between about 20 and about 60 carbon atoms, mostpreferably between about 30 and about 50 carbon atoms. Suitable examplesof long-chain alcohol waxes include but are not limited to alcohol waxescommercially available from Baker Hughes under the Performacol tradename such as, for example, Performacol 350, 425 and 550. Mostpreferably, the long-chain alcohol wax has a melting temperature rangefrom about 93° C. to about 105° C.

According to preferred embodiments, the long-chain alcohol wax ispresent in the composition in an amount ranging from 0.1% to 50% byweight relative to the total weight of the composition. Preferably, thelong-chain alcohol wax is present in an amount ranging from 0.1% to 20%by weight relative to the total weight of the composition, and morepreferably from 0.1% to 10%. One of ordinary skill in the art willrecognize that the long-chain alcohol wax of the present invention maybe commercially available, and may come from suppliers in the form of adilute solution. The amounts of the long-chain alcohol wax disclosedherein therefore reflect the weight percent of active material.

According to particularly preferred embodiments, the weight fraction oflong-chain alcohol wax to ethylene polymer wax is from about 0.005 toabout 0.1 (that is, about 0.5:99.5 to about 10:90 ratio of long-chainalcohol wax to ethylene polymer wax(es)), with about 0.01 to about 0.03being most preferred.

Volatile Silicone Oil

The composition of the present invention may optionally contain at leastone volatile silicone oil. According to preferred embodiments of thepresent invention, the composition further comprises at least onevolatile silicone oil. According to particularly preferred embodiments,the composition further comprises at least one cyclic volatile siliconeoil.

Suitable volatile silicone oils include but are not limited to linear orcyclic silicone oils having a viscosity at room temperature less than orequal to 6cSt and having from 2 to 7 silicon atoms, these siliconesbeing optionally substituted with alkyl or alkoxy groups of 1 to 10carbon atoms. Specific oils that may be used in the invention includeoctamethyltetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane,hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxaneand their mixtures. Other volatile oils which may be used include KF 96Aof 6 cSt viscosity, a commercial product from Shin Etsu having a flashpoint of 94° C. Preferably, the volatile silicone oils have a flashpoint of at least 40° C.

Non-limiting examples of volatile silicone oils are listed in Table 1below.

TABLE 1 Flash Point Viscosity Compound (° C.) (cSt) Octyltrimethicone 931.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2(cyclopentasiloxane or D5) Octamethylcyclotetrasiloxane 55 2.5(cyclotetradimethylsiloxane or D4) Dodecamethylcyclohexasiloxane (D6) 937 Decamethyltetrasiloxane (L4) 63 1.7 KF-96 A from Shin Etsu 94 6 PDMS(polydimethylsiloxane) DC 200 56 1.5 (1.5 cSt) from Dow Corning PDMS DC200 (2 cSt) from Dow Corning 87 2 PDMS DC 200 (5 cSt) from Dow Corning134 5 PDMS DC 200 (3 St) from Dow Corning 102 3

If present, the volatile silicone oil is preferably present in an amountof about 0.1-80 percent by weight, more preferably from about 5 to about60 percent by weight, even more preferably from 5 to about 50 percent byweight and most preferably from about 5 to about 20 percent by weight ofthe total weight of the composition. All numerical ranges and subrangesare included within the numerical ranges identified above.

The compositions of the invention can also optionally comprise anyadditive usually used in such compositions. For example, oils,organogelators, dispersants, antioxidants, vitamins, emollients,preserving agents, fragrances, waxes, fillers, neutralizing agents,cosmetic and dermatological active agents, moisturizers, humectants,water, sunscreen agents, gelling agents, elastomers, short chain esters,surfactants, plasticizers, and mixtures thereof can be added, ifdesired. Further examples of suitable optional components can be foundin the references which have been incorporated by reference in thisapplication. Still further examples of such additional ingredients maybe found in the International Cosmetic Ingredient Dictionary andHandbook (9^(th) ed. 2002).

A person skilled in the art will take care to select the optionaladditional additives and/or the amount thereof such that theadvantageous properties of the compositions, kits and methods accordingto the invention are not, or are not substantially, adversely affectedby the envisaged addition.

Such additives may be present in the composition in a proportion from 0%to 90% relative to the total weight of the composition, preferably from0.01% to 85%, and most preferably from 10 to 80% (if present).

Specific examples of acceptable optional ingredients include but are notlimited to non-volatile silicone oils such as, for example, non-volatilelinear polydimethylsiloxanes (PDMSs) such as dimethicones;polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, whichare pendent and/or at the end of a silicone chain, these groups eachcontaining from 2 to 24 carbon atoms; and phenylated silicones, forinstance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyl trisiloxanes and 2-phenylethyl tri methylsiloxysilicates.

Suitable non-silicone, non-volatile oils include but are not limited topolar oils such as:

hydrocarbon-based plant oils with a high triglyceride content consistingof fatty acid esters of glycerol, the fatty acids of which may havevaried chain lengths, these chains possibly being linear or branched,and saturated or unsaturated; these oils are especially wheat germ oil,corn oil, sunflower oil, karite butter, castor oil, sweet almond oil,macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil,alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil,avocado oil, hazelnut oil, grape seed oil, blackcurrant seed oil,evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, ryeoil, safflower oil, candlenut oil, passion flower oil or musk rose oil;or caprylic/capric acid triglycerides, for instance those sold by thecompany Stearineries Dubois or those sold under the names Miglyol 810,812 and 818 by the company Dynamit Nobel;

synthetic oils or esters of formula R₅COOR₆ in which R₅ represents alinear or branched higher fatty acid residue containing from 1 to 40carbon atoms, including from 7 to 19 carbon atoms, and R₆ represents abranched hydrocarbon-based chain containing from 1 to 40 carbon atoms,including from 3 to 20 carbon atoms, with R₆+R₇≧10, such as, forexample, Purcellin oil (cetostearyl octanoate), isononyl isononanoate,C₁₂ to C₁₅ alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate,and octanoates, decanoates or ricinoleates of alcohols or ofpolyalcohols; hydroxylated esters, for instance isostearyl lactate ordiisostearyl malate; and pentaerythritol esters;

synthetic ethers containing from 10 to 40 carbon atoms;

C₈ to C₂₆ fatty alcohols, for instance oleyl alcohol; and

mixtures thereof.

Suitable elastomers include but are not limited to crosslinkedelastomeric polyorganosiloxane which can can bear hydrophile groups,such as polyoxyethylene or copoly(oxyethylene/oxypropylene), if desired.Such elastomeric silicones may also optionally have hydrophile groups inthe crosslinking chain.

Suitable crosslinked elastomeric polyorganosiloxanes include, but arenot limited to, the crosslinked elastomeric polyorganosiloxanesdescribed in application EP-A-0,295,886, the disclosure of which isincorporated herein by reference. According to that application, theelastomers are obtained by addition reaction and crosslinking, in thepresence of a platinum-type catalyst, of at least:

(a) a polyorganosiloxane having at least two C₂ to C₆ lower alkenylgroups per molecule; and

(b) a polyorganosiloxane having at least two hydrogen atoms linked to asilicon atom per molecule.

Suitable elastomers also include but are not limited to those describedin U.S. Pat. No. 5,266,321, the disclosure of which is incorporated byreference herein. According to that patent, the elastomers are chosen inparticular from:

i) polyorganosiloxanes comprising R₂SiO and RSiO_(1.5) units andoptionally R₃SiO_(0.5) and/or SiO₂ units in which the radicals R,independently of each other, are chosen from a hydrogen, an alkyl suchas methyl, ethyl or propyl, an aryl such as phenyl or tolyl, anunsaturated aliphatic group such as vinyl, the weight ratio of the unitsR₂SiO to the units RSiO_(1.5) ranging from 1/1 to 30/1;

ii) polyorganosiloxanes which are insoluble and swellable in siliconeoil, obtained by addition of an polyorganohydrogenosiloxane (1) and of apolyorganosiloxane (2) having unsaturated aliphatic groups such that theamount of hydrogen or of unsaturated aliphatic groups in (1) and (2)respectively ranges from 1 to 20 mol % when the polyorganosiloxane isnon-cyclic and from 1 to 50 mol % when the polyorganosiloxane is cyclic.Optionally, these polyorganosiloxanes can comprise from 1 to 40oxyalkylene groups, such as oxypropylene and/or oxyethylene groups.

Specific examples of elastomeric polyorganosiloxanes which can be usedaccording to the invention include those sold or made under the namesKSG6 from Shin-Etsu, Trefil E-505C, Trefil E-506C, DC 9506 or DC 9701from Dow-Corning, Gransil from Grant Industries (SR-CYC, SR DMF10,SR-DC556) or those marketed in the form of preconstituted gels (DC9040,DC9041 from Dow Corning, KSG15, KSG17, KSG16, KSG18, KSG21 fromShin-Etsu, Gransil SR 5CYC gel, Gransil SR DMF 10 gel, Gransil SR DC556gel, SF 1204 and JK 113 from General Electric) or emulsifying elastomerssuch as those sold under the names of KSG-210, KSG-30, KSG-31, KSG-32,KSG-33, KSG-40, KSG 41, KSG-42, KSG-43, KSG-44 and KSG-710 fromShin-Etsu, or coated elastomers such as products sold under thedenomination KSP (for example, KSP100, KSP 200, KSP 300) sold by ShinEtsu and/or those described in U.S. Pat. No. 5,538,793, the disclosureof which is hereby incorporated by reference. A mixture of thesecommercial products may also be used.

If present, the elastomeric compounds are preferably present in anamount of 0.1-25 percent by weight, more preferably from 0.5 to 20percent by weight, even more preferably from 1 to 15 percent by weightand most preferably from 3 to 10 percent by weight of the total weightof the composition. One of ordinary skill in the art will recognize thatthe elastomeric compound may be commercially available, and may comefrom suppliers in the form of a dilute solution. In such case, theamounts of the elastomer disclosed herein therefore reflect the weightpercent of active material. All numerical ranges and subranges areincluded within the numerical ranges identified above.

The composition according to the invention can be in the form of atinted or non tinted dermatological composition or a care compositionfor keratin materials such as the skin, the hair, the lips and/orsuperficial body growths, in the form of an antisun composition ormake-up-removing product in stick form. It can be used in particular asa care base for the skin, superficial body growths or the lips (lipbalms, for protecting the lips against cold and/or sunlight and/or thewind, or care cream for the skin, the nails or the hair).

The composition of the invention may also be in the form of a coloredmake-up product for the skin, in particular a foundation, optionallyhaving care or treating properties, a blusher, a face powder, an eyeshadow, a concealer product, an eyeliner, a make-up product for thebody; a make-up product for the lips such as a lipstick, optionallyhaving care or treating properties; a make-up product for superficialbody growths such as the nails or the eyelashes, in particular in theform of a mascara cake, or for the eyebrows and the hair, in particularin the form of a pencil.

Needless to say, the composition of the invention should be cosmeticallyor dermatologically acceptable, i.e., it should contain a non-toxicphysiologically acceptable medium and should be able to be applied tothe skin, superficial body growths or the lips of human beings. For thepurposes of the invention, the expression “cosmetically acceptable”means a composition of pleasant appearance, odor, feel and/or taste.

According to preferred embodiments of the present invention, methods oftreating, caring for and/or making up keratinous material such as skin,lips, hair and mucous membranes by applying compositions of the presentinvention to the keratinous material in an amount sufficient to treat,care for and/or make up the keratinous material are provided.

According to other preferred embodiments, methods of covering or hidingdefects associated with keratinous material such as imperfections ordiscolorations by applying compositions of the present invention to thekeratinous material in an amount sufficient to cover or hide suchdefects are provided.

According to yet other preferred embodiments, methods of enhancing theappearance of keratinous material by applying compositions of thepresent invention to the keratinous material in an amount sufficient toenhance the appearance of the keratinous material are provided.

In accordance with the three preceding preferred embodiments, thecompositions of the present invention are applied topically to thedesired area of the skin in an amount sufficient to treat, care forand/or make up the keratinous material, to cover or hide defectsassociated with keratinous material, skin imperfections ordiscolorations, or to enhance the appearance of keratinous material. Thecompositions may be applied to the desired area as needed, preferablyonce or twice daily, more preferably once daily and then preferablyallowed to dry before subjecting to contact such as with clothing orother objects. The composition is preferably applied to the desired areathat is dry or has been dried prior to application.

According to a preferred embodiment of the present invention,compositions having improved cosmetic properties such as, for example,improved long wear, transfer resistance or waterproof properties areprovided. The improved properties may also be chosen from improvedflexibility, wearability, drying time or retention as well as reducedtackiness or migration over time.

In accordance with yet another embodiment of the present invention, kitscomprising a composition comprising at least onepolyorganosiloxane-containing polymer, at least one volatilenon-silicone oil, at least one ethylene polymer wax, at least onesilicone film-forming agent and, optionally, at least one long-chainalcohol wax, at least one coloring agent, and/or at least one volatilesilicone oil are provided. In addition to this composition, the kits ofthe present invention can further comprise one or more compositions suchas, for example, compositions to be applied on top of make-upcompositions (for example, glosses or topcoats), compositions to beapplied underneath make-up compositions (for example, primers orbasecoats), and compositions for removing make-up from keratinmaterials. Any suitable topcoat, basecoat or removal composition can beincluded in such kits.

The packaging and application device for any such kit or compositions inthe kit may be chosen and manufactured by persons skilled in the art onthe basis of their general knowledge, and adapted according to thenature of the compositions to be packaged. Indeed, the type of device tobe used can be in particular linked to the consistency of thecomposition, in particular to its viscosity; it can also depend on thenature of the constituents present in the compositions.

Unless otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective measurements. The following examples are intended toillustrate the invention without limiting the scope as a result. Thepercentages are given on a weight basis.

Example 1 Sample Compositions

Composition A Composition B Composition C Composition D Composition ESeq Trade Name INCI Name % w/w % w/w % w/w % w/w % w/w A PERMETHYLISODODECANE 36.62 33.12 21.62 18.40 29.40 99A DC245 Cyclopentasiloxane0.00 0.00 15.00 13.00 0.00 SR 1000 trimethylsyloxysilicate 11.80 12.3011.80 12.32 12.32 DC 2-8179 NYLON-611/DIMETHICONE 10.00 12.50 10.0012.70 12.70 GELLANT- COPOLYMER BATCH # PE02121867 58.42 57.92 58.4256.42 54.42 C Red Iron Oxide Iron Oxides 0.58 0.58 0.58 0.58 0.58 yellow5 Al yellow 5 Al lake 0.66 0.66 0.66 0.66 0.66 Lake FDC yellow 6 yellow6 0.64 0.64 0.64 0.64 0.64 Al Lake DC Red 7 W Red 7 Lake 0.78 0.78 0.780.78 0.78 blue 1 lake blue 1 0.06 0.06 0.06 0.06 0.06 black iron IronOxides 0.14 0.14 0.14 0.14 0.14 oxide titanium titanium dioxide 0.770.77 0.77 0.77 0.77 dioxide Bentone gel ISD V DISTEARDIMONIUM 10.0010.00 10.00 10.00 10.00 HECTORITE/isododecane/propylene carbonate10/87/3 SR 1000 trimethylsyloxysilicate 3.20 3.20 3.20 3.20 3.20PERMETHYL ISODODECANE 5.25 5.25 5.25 5.25 5.25 99A 22.08 22.08 22.0822.08 22.08 D Gemtone Ruby Mica and Titanium dioxide 4.50 4.50 4.50 4.504.50 G 010 and Iron oxides and Carmine Sunsphere Silica Silica 0.00 2.000.00 2.00 2.00 Beady bead Aluminium Calcium Sodium Silicate 0.00 2.000.00 0.00 2.00 MICA CONCORD MICA 0.00 0.00 0.00 2.00 2.00 1000 4.50 8.504.50 8.50 10.50 B Performalene 400 polyethylene 6.00 6.00 6.00 5.20 5.20Polywax500 polyethylene 9.00 4.50 9.00 7.80 7.80 performacol 550 C30-50alcohols 0 1.00 0 0.00 0.00 alcohol 15.00 11.50 15.00 13.00 13.00 100.00100.00 100.00 100.00 100.00 HARDNESS (g) 33 68 52 61 53 Wear 80 75 73 8490Procedure of Preparing compositions

-   1. Combine Phase A ingredients together, then transfer to the beaker    to a 100° C. oil bath and mix with a propeller mixer until the    solution completely uniform.-   2. Combine Phase B ingredients together into Phase A, then mix until    the waxes melted.-   3. Add Phase C ingredients into Phase (A+B) solution and mix for    about 10 minutes with high speed of mixer rotation.-   4. Add phase D into phase(A+B+C) and mix with high speed for 15    minutes.-   5. Reduce temperature down to 90-95° C., continue mixing at low    speed, for 5-10 minutes-   6. Transfer the resulting fluid to the mold at room temperature.-   7. After cool at room temperature about 10 minutes, put the mold in    the freezer for 40 minutes.

Procedure of Preparing Phase C (Color Grind)

-   1. Combine Phase C ingredients together, then mix by hand until    pigments are totally wet, then use high speed mixer to mix about 10    minutes.-   2. Transfer the mixture to the Disconti-Mill and mill for 1 hour    until the color grind becomes homogeneous.-   3. Transfer the color grind phase C into the container for use in    the procedure above.

Procedure for Determining Hardness

The procedure used for determining hardness is set forth in paragraph[0022] above.

Procedure for Determining Wear

The lip compositions were applied to the lips of 6 panelists. The lipswere photographed before, and immediately after, application usingdiffuse lighting in a device such as the one described and claimed inUS20030067545, the entire contents of which are incorporated byreference, and the images analyzed for L* color value. The L* colorvalue indicates the darkness or intensity of the color. The panelistswere then asked to eat a meal consisting of a sandwich, a salad and ahot beverage. The lips of the panelists were photographed after the mealusing the device above, and the images analyzed for L* color value. Thewear is reported as % wear and indicates how much of the compositionremains on the lips.

Example 2

Seq Trade Name INCI Name Composition F Composition G A PERMETHYL 99AISODODECANE 12.00 12.00 DC 245 Fluid Cyclopentasiloxane 18.02 15.61 SR1000 trimethylsyloxysilicate 6.00 8.00 DC 2-8179 GELLANT- NYLON- 2.573.48 BATCH # 2121867 611/DIMETHICONE COPOLYMER PERFORMAL 400polyethylene 5.20 4.80 Polywax500 polyethylene 1.20 1.10 B MT-100-ZTITANIUM DIOXIDE + 5.50 5.50 STEARIC ACID + ALUMINUM HYDROXIDE (74/13/13ITT-Titanium Dioxide ITT-Titanium Dioxide 7.54 7.54 ITT-Iron Oxide -ITT-Iron Oxides 2.06 2.06 Yellow ITT-Iron Oxide - Red ITT-Iron Oxides(and) 0.72 0.72 Iron Oxides ITT-Iron Oxide - Blue ITT-Iron Oxides (and)0.68 0.68 ULTRAMARINE DC 245 Fluid Cyclopentasiloxane 26.40 26.40 DC9701 powder DIMETHICONE 1.10 1.10 CROSSPOLYMER/silica pigment paste577-52-5 44.00 44.00 C LUXSIL CALCIUM SODIUM 7.00 7.00 BOROSILICATEGANZPEARL GMP METHYL METHACRYLATE 3.50 3.50 0820 CROSSPOLYMER SunsphereSilica SILICA 0.50 0.50 total = 100.00 100.00

Procedure of Preparing Compositions

The compositions were prepared using the same procedures as set forth inexample 1, except that step 4 was omitted.

1. A solid composition comprising at least onepolyorganosiloxane-containing copolymer, at least one volatilenon-silicone oil, at least one ethylene homopolymer wax, at least onelong-chain alcohol wax, and at least one silicone resin film formingagent.
 2. The composition according to claim 1, wherein thepolyorganosiloxane-containing copolymer comprises at least onehydrocarbon-based moiety comprising an amide group.
 3. The compositionaccording to claim 2, wherein the polyorganosiloxane-containingcopolymer is a Nylon-611/dimethicone copolymer.
 4. The compositionaccording to claim 1, wherein the volatile non-silicone oil is avolatile hydrocarbon oil.
 5. The composition according to claim 4,wherein the volatile hydrocarbon oil is an isoparaffin.
 6. Thecomposition according to claim 5, wherein the isoparaffin isisododecane.
 7. The composition according to claim 1, wherein thecomposition further comprises at least one long-chain alcohol wax havingan average carbon chain length of between about 20 and about 60 carbonatoms.
 8. The composition according to claim 1, wherein the compositionfurther comprises at least one coloring agent.
 9. The compositionaccording to claim 1, wherein the silicone resin film forming agent isan MK or MQ resin.
 10. The composition according to claim 9, wherein thesilicone resin film forming agent is an MQ resin.
 11. The compositionaccording to claim 3, wherein the long-chain alcohol wax has an averagecarbon chain length of between about 20 and about 60 carbon atoms. 12.The composition according to claim 11, wherein the long-chain alcoholwax has an average carbon chain length of between about 30 and about 50carbon atoms.
 13. The composition according to claim 10, furthercomprising a long-chain alcohol wax having an average carbon chainlength of between about 20 and about 60 carbon atoms.
 14. Thecomposition according to claim 13, wherein the long-chain alcohol waxhas an average carbon chain length of between about 30 and about 50carbon atoms.
 15. The composition according to claim 1, wherein theethylene homopolymer wax has an average molecular weight of betweenabout 200 and about
 1500. 16. The composition according to claim 15,wherein the ethylene homopolymer wax has an average molecular weight ofbetween about 400 and about
 700. 17. The composition according to claim1, further comprising at least one volatile silicone oil.
 18. Thecomposition according to claim 1, further comprising at least one cyclicvolatile silicone oil.
 19. The composition according to claim 1, in theform of a lipstick.
 20. The composition according to claim 1, in theform of a foundation.